CN114044944B - High-strength tear-resistant rubber material for ships and preparation method thereof - Google Patents
High-strength tear-resistant rubber material for ships and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to the field of high polymer materials, in particular to a high-strength tear-resistant rubber material for ships and a preparation method thereof, wherein the high-strength tear-resistant rubber material comprises the following components: the rubber material prepared by the invention has good mechanical property, high tensile strength and tear strength, good salt spray corrosion resistance and small density, and is suitable for manufacturing marine rubber parts.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-strength tear-resistant rubber material for ships and a preparation method thereof.
Background
The natural rubber is used as one of renewable natural resources, has high strength, easy vulcanization, excellent comprehensive performance of products, high strength, good elasticity, low creep, large elongation, good wear resistance and the like, is widely applied to various fields of aerospace, automobile tires, medical elastomers, chemical industry and the like, and plays a great role in the development of global economy.
However, in some practical applications, such as ocean shipping, the tear resistance and salt spray corrosion resistance of natural rubber have not been satisfactory and need to be improved.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical development requirements, the invention provides a high-strength tear-resistant rubber material for ships and a preparation method thereof.
The adopted technical scheme is as follows:
a high-strength tear-resistant rubber material for ships comprises the following components:
natural rubber, epoxidized natural rubber, aminated solution polymerized styrene-butadiene rubber, liquid polyisoprene rubber, epoxidized butadiene rubber, coupling agent modified one-dimensional carbon nano-material, white carbon black, zinc oxide and auxiliary agent.
Further, the composition comprises the following components in parts by weight:
40-60 parts of natural rubber, 5-10 parts of epoxidized natural rubber, 20-30 parts of aminated solution-polymerized styrene-butadiene rubber, 20-30 parts of liquid polyisoprene rubber, 10-15 parts of epoxidized butadiene rubber, 15-20 parts of coupling agent modified one-dimensional carbon nano material, 5-8 parts of white carbon black, 5-8 parts of carbon black, 5-10 parts of zinc oxide and 0.1-1 part of auxiliary agent.
Further, the preparation method of the aminated solution polymerized styrene-butadiene rubber comprises the following steps:
under the protection of inert gas, uniformly mixing butadiene, styrene, an amination reagent and cyclohexane, diluting butyl lithium with tetrahydrofuran, adding the diluted butyl lithium, controlling the reaction temperature to be 45-50 ℃, reacting for 8-12h, performing wet devolatilization, and drying.
Further, the mass ratio of butyl lithium to tetrahydrofuran was 1: 60-80.
Further, the amination reagent is 4-aminostyrene, 4-dimethylaminostyrene or 1, 1-bis (4-dimethylaminophenyl) ethylene, preferably 4-aminostyrene.
Further, the preparation method of the epoxidized butadiene rubber comprises the following steps:
adding butadiene rubber into cyclohexane, adding formic acid and polyethylene glycol, stirring, adding hydrogen peroxide, reacting at 70-75 deg.C for 1.5-2 hr, recovering to room temperature, precipitating with ethanol, filtering, washing the obtained solid with water to neutrality, and drying.
Further, the coupling agent modified one-dimensional carbon nano material is a coupling agent modified carbon nano tube or a coupling agent modified carbon nano fiber.
Further, the coupling agent is a coupling agent KH-550, KH-560 or KH-570;
the method for modifying the one-dimensional carbon nano material by the coupling agent comprises the following steps:
adding the one-dimensional carbon nano material into an ethanol/water mixed solvent, uniformly mixing, heating to 60-65 ℃, adding the hydrolyzed coupling agent, keeping the temperature for reaction for 20-40min, filtering, and drying the obtained solid.
Further, the auxiliary agent comprises sulfur, a vulcanizing agent DCP, an accelerator NS, an accelerator DM, an antioxidant KY-616 and an antioxidant 802.
The invention also provides a preparation method of the marine high-strength tear-resistant rubber material, which comprises the following specific steps:
mixing and plasticating natural rubber, epoxidized natural rubber, aminated solution-polymerized styrene-butadiene rubber and epoxidized butadiene rubber, mixing and banburying the mixture with liquid polyisoprene rubber, white carbon black and carbon black for 30-90s, adding a coupling agent modified one-dimensional carbon nano material, zinc oxide and an auxiliary agent, continuously banburying for 180-240s, thinly passing and wrapping a piece by a triangular bag, standing for 12-24h, and vulcanizing at 140-150 ℃ and 10-15MPa for 10-20 min.
The invention has the beneficial effects that:
the natural rubber has the advantages of high strength, good elasticity, low creep, high elongation, good wear resistance and the like, and has excellent comprehensive performance, but the natural rubber has poor tear resistance and corrosion resistance, so the application of the natural rubber is limited to a certain extent;
the epoxidized natural rubber is prepared by reacting natural rubber under a peracid condition, and has excellent solvent resistance and gas barrier property besides retaining the excellent performance of the natural rubber;
the liquid polyisoprene rubber is an isoprene oligomer, is a non-toxic, tasteless and colorless viscous substance, can be used as a reactive plasticizer to be mixed and dissolved with various rubbers such as natural rubber, epoxidized natural rubber, styrene butadiene rubber and the like after being added, improves the crosslinking degree of the rubber material, improves the overall performance, can also improve the interface performance, and promotes the dispersion of the coupling agent modified one-dimensional carbon nano material, white carbon black, carbon black and zinc oxide;
the amine group in the aminated solution polymerized styrene-butadiene rubber can be grafted with epoxy groups in the epoxidized natural rubber and the epoxidized butadiene rubber amine group in a covalent form, so that the crosslinking density of the rubber material is improved, and the interface bonding performance is improved;
tests prove that the rubber material prepared by the invention has good mechanical property, high tensile strength and tear strength, good salt spray corrosion resistance and low density, and is suitable for manufacturing marine rubber parts.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
the high-strength tear-resistant rubber material for the ship comprises the following components in parts by weight:
50 parts of natural rubber, 10 parts of epoxidized natural rubber, 20 parts of aminated solution-polymerized styrene-butadiene rubber, 25 parts of liquid polyisoprene rubber, 12 parts of epoxidized butadiene rubber, 20 parts of coupling agent KH-550 modified carbon nano tube, 5 parts of white carbon black, 5 parts of carbon black, 10 parts of zinc oxide, 0.5 part of sulfur, 0.1 part of vulcanizing agent DCP, 0.1 part of accelerator NS, 0.1 part of accelerator DM, KY-6160.1 parts of antioxidant and 8020.1 parts of antioxidant.
The preparation method of the aminated solution-polymerized styrene-butadiene rubber comprises the following steps:
under the protection of nitrogen, uniformly mixing butadiene, styrene, 4-aminostyrene and cyclohexane, diluting butyl lithium with tetrahydrofuran, and adding the diluted butyl lithium and tetrahydrofuran, wherein the mass ratio of the butyl lithium to the tetrahydrofuran is 1: 60, controlling the reaction temperature to be 45 ℃, carrying out wet devolatilization after 10h of reaction, and drying.
The preparation method of the epoxidized butadiene rubber comprises the following steps:
adding butadiene rubber into cyclohexane, adding formic acid and polyethylene glycol, stirring, adding hydrogen peroxide, reacting at 75 deg.C for 2 hr, recovering to room temperature, precipitating with ethanol, filtering, washing the obtained solid with water to neutrality, and drying.
The method for modifying the carbon nano tube by the coupling agent KH-550 comprises the following steps:
mixing KH-550 with water, performing ultrasonic treatment for 0.5h, adding methanol, performing ultrasonic treatment for 0.5h to obtain hydrolyzed KH-550, and adding carbon nanotubes into ethanol/water at a mass ratio of 1: 1, uniformly mixing the components in a mixed solvent consisting of 1, heating to 65 ℃, adding hydrolyzed KH-550, keeping the temperature for reaction for 40min, filtering, and drying the obtained solid.
The preparation method of the marine high-strength tear-resistant rubber material comprises the following steps:
mixing and plasticating natural rubber, epoxidized natural rubber, aminated solution-polymerized styrene-butadiene rubber and epoxidized butadiene rubber, mixing and banburying the mixture with liquid polyisoprene rubber, white carbon black and carbon black for 60s, adding a coupling agent KH-550 modified carbon nanotube, zinc oxide, sulfur, a vulcanizing agent DCP, an accelerator NS, an accelerator DM, an antioxidant KY-616 and an antioxidant 802, continuously banburying for 240s, thinly passing and wrapping the mixture into a triangular bag, standing for 24h, and vulcanizing at 150 ℃ and 15MPa for 15 min.
Example 2:
a high-strength tear-resistant rubber material for ships comprises the following components in parts by weight:
60 parts of natural rubber, 5 parts of epoxidized natural rubber, 20 parts of aminated solution-polymerized styrene-butadiene rubber, 25 parts of liquid polyisoprene rubber, 10 parts of epoxidized butadiene rubber, 15 parts of coupling agent KH-550 modified carbon nano tube, 6 parts of white carbon black, 6 parts of carbon black, 8 parts of zinc oxide, 0.5 part of sulfur, 0.1 part of vulcanizing agent DCP, 0.1 part of accelerator NS, 0.1 part of accelerator DM, KY-6160.1 parts of antioxidant and 8020.1 parts of antioxidant.
The preparation method of the aminated solution-polymerized styrene-butadiene rubber comprises the following steps:
under the protection of nitrogen, uniformly mixing butadiene, styrene, 4-aminostyrene and cyclohexane, diluting butyl lithium with tetrahydrofuran, and adding the diluted butyl lithium and tetrahydrofuran, wherein the mass ratio of the butyl lithium to the tetrahydrofuran is 1: 65, controlling the reaction temperature to be 50 ℃, carrying out wet devolatilization after reacting for 12 hours, and drying.
The preparation method of the epoxidized butadiene rubber comprises the following steps:
adding butadiene rubber into cyclohexane, adding formic acid and polyethylene glycol, stirring, adding hydrogen peroxide, reacting at 70 deg.C for 1.5h, recovering to room temperature, precipitating with ethanol, filtering, washing the obtained solid with water to neutrality, and drying.
The method for modifying the carbon nano tube by the coupling agent KH-550 comprises the following steps:
mixing KH-550 with water, performing ultrasonic treatment for 0.5h, adding methanol, performing ultrasonic treatment for 0.5h to obtain hydrolyzed KH-550, and adding carbon nanotubes into ethanol/water at a mass ratio of 1: 1, uniformly mixing the components in a mixed solvent consisting of 1, heating to 65 ℃, adding hydrolyzed KH-550, keeping the temperature for reaction for 40min, filtering, and drying the obtained solid.
The preparation method of the marine high-strength tear-resistant rubber material comprises the following steps:
mixing and plasticating natural rubber, epoxidized natural rubber, aminated solution-polymerized styrene-butadiene rubber and epoxidized butadiene rubber, mixing and banburying the mixture with liquid polyisoprene rubber, white carbon black and carbon black for 50s, adding a coupling agent KH-550 modified carbon nano tube, zinc oxide, sulfur, a vulcanizing agent DCP, an accelerator NS, an accelerator DM, an antioxidant KY-616 and an antioxidant 802, continuously banburying for 240s, thinly passing and wrapping the mixture into a triangular bag, standing for 24h, and vulcanizing at 140 ℃ and 10MPa for 15 min.
Example 3:
a high-strength tear-resistant rubber material for ships comprises the following components in parts by weight:
60 parts of natural rubber, 10 parts of epoxidized natural rubber, 30 parts of aminated solution-polymerized styrene-butadiene rubber, 30 parts of liquid polyisoprene rubber, 15 parts of epoxidized butadiene rubber, 20 parts of coupling agent KH-550 modified carbon nano tube, 8 parts of white carbon black, 8 parts of carbon black, 0 part of zinc oxide, 0.5 part of sulfur, 0.1 part of vulcanizing agent DCP, 0.1 part of accelerator NS, 0.1 part of accelerator DM, KY-6160.1 parts of antioxidant and 8020.1 parts of antioxidant.
The preparation method of the aminated solution-polymerized styrene-butadiene rubber comprises the following steps:
under the protection of nitrogen, uniformly mixing butadiene, styrene, 4-aminostyrene and cyclohexane, diluting butyl lithium with tetrahydrofuran, and adding the diluted butyl lithium and tetrahydrofuran, wherein the mass ratio of the butyl lithium to the tetrahydrofuran is 1: 80, controlling the reaction temperature at 50 ℃, carrying out wet devolatilization after 12h of reaction, and drying.
The preparation method of the epoxidized butadiene rubber comprises the following steps:
adding butadiene rubber into cyclohexane, adding formic acid and polyethylene glycol, stirring, adding hydrogen peroxide, reacting at 75 deg.C for 2 hr, recovering to room temperature, precipitating with ethanol, filtering, washing the obtained solid with water to neutrality, and drying.
The method for modifying the carbon nano tube by the coupling agent KH-550 comprises the following steps:
mixing KH-550 with water, performing ultrasonic treatment for 0.5h, adding methanol, performing ultrasonic treatment for 0.5h to obtain hydrolyzed KH-550, and adding carbon nanotubes into ethanol/water at a mass ratio of 1: 1, uniformly mixing the components in a mixed solvent consisting of 1, heating to 65 ℃, adding hydrolyzed KH-550, keeping the temperature for reaction for 40min, filtering, and drying the obtained solid.
The preparation method of the marine high-strength tear-resistant rubber material comprises the following steps:
mixing and plasticating natural rubber, epoxidized natural rubber, aminated solution-polymerized styrene-butadiene rubber and epoxidized butadiene rubber, mixing and banburying the mixture with liquid polyisoprene rubber, white carbon black and carbon black for 90s, adding a coupling agent KH-550 modified carbon nanotube, zinc oxide, sulfur, a vulcanizing agent DCP, an accelerator NS, an accelerator DM, an antioxidant KY-616 and an antioxidant 802, continuously banburying for 240s, thinly passing and wrapping the mixture into a triangular bag, standing for 24h, and vulcanizing at 150 ℃ and 15MPa for 20 min.
Example 4:
a high-strength tear-resistant rubber material for ships comprises the following components in parts by weight:
60 parts of natural rubber, 5 parts of epoxidized natural rubber, 30 parts of aminated solution-polymerized styrene-butadiene rubber, 20 parts of liquid polyisoprene rubber, 15 parts of epoxidized butadiene rubber, 15 parts of coupling agent KH-550 modified carbon nano tube, 8 parts of white carbon black, 5 parts of carbon black, 10 parts of zinc oxide, 0.5 part of sulfur, 0.1 part of vulcanizing agent DCP, 0.1 part of accelerator NS, 0.1 part of accelerator DM, KY-6160.1 parts of antioxidant and 8020.1 parts of antioxidant.
The preparation method of the aminated solution-polymerized styrene-butadiene rubber comprises the following steps:
under the protection of nitrogen, uniformly mixing butadiene, styrene, 4-aminostyrene and cyclohexane, diluting butyl lithium with tetrahydrofuran, and adding the diluted butyl lithium and tetrahydrofuran, wherein the mass ratio of the butyl lithium to the tetrahydrofuran is 1: 60, controlling the reaction temperature to be 50 ℃, carrying out wet devolatilization after 8 hours of reaction, and drying.
The preparation method of the epoxidized butadiene rubber comprises the following steps:
adding butadiene rubber into cyclohexane, adding formic acid and polyethylene glycol, stirring, adding hydrogen peroxide, reacting at 75 deg.C for 1.5h, recovering to room temperature, precipitating with ethanol, filtering, washing the obtained solid with water to neutrality, and drying.
The method for modifying the carbon nano tube by the coupling agent KH-550 comprises the following steps:
mixing KH-550 with water, performing ultrasonic treatment for 0.5h, adding methanol, performing ultrasonic treatment for 0.5h to obtain hydrolyzed KH-550, and adding carbon nanotubes into ethanol/water at a mass ratio of 1: 1, uniformly mixing the components in a mixed solvent consisting of 1, heating to 65 ℃, adding hydrolyzed KH-550, keeping the temperature for reaction for 20min, filtering, and drying the obtained solid.
The preparation method of the marine high-strength tear-resistant rubber material comprises the following steps:
mixing and plasticating natural rubber, epoxidized natural rubber, aminated solution-polymerized styrene-butadiene rubber and epoxidized butadiene rubber, mixing and banburying the mixture with liquid polyisoprene rubber, white carbon black and carbon black for 90s, adding a coupling agent KH-550 modified carbon nano tube, zinc oxide, sulfur, a vulcanizing agent DCP, an accelerator NS, an accelerator DM, an antioxidant KY-616 and an antioxidant 802, continuously banburying for 240s, thinly passing, wrapping by a triangular bag, standing for 24h, and vulcanizing at 140 ℃ and 15MPa for 10 min.
Example 5:
the high-strength tear-resistant rubber material for the ship comprises the following components in parts by weight:
50 parts of natural rubber, 10 parts of epoxidized natural rubber, 30 parts of aminated solution-polymerized styrene-butadiene rubber, 30 parts of liquid polyisoprene rubber, 10 parts of epoxidized butadiene rubber, 15 parts of coupling agent KH-560 modified carbon fiber, 8 parts of white carbon black, 8 parts of carbon black, 5 parts of zinc oxide, 0.5 part of sulfur, 0.1 part of vulcanizing agent DCP, 0.1 part of accelerator NS, 0.1 part of accelerator DM, KY-6160.1 parts of antioxidant and 8020.1 parts of antioxidant.
The preparation method of the aminated solution-polymerized styrene-butadiene rubber comprises the following steps:
under the protection of nitrogen, uniformly mixing butadiene, styrene, 4-aminostyrene and cyclohexane, diluting butyl lithium with tetrahydrofuran, and adding the diluted butyl lithium and tetrahydrofuran, wherein the mass ratio of the butyl lithium to the tetrahydrofuran is 1: 60, controlling the reaction temperature to be 50 ℃, carrying out wet devolatilization after 10h of reaction, and drying.
The preparation method of the epoxidized butadiene rubber comprises the following steps:
adding butadiene rubber into cyclohexane, adding formic acid and polyethylene glycol, stirring, adding hydrogen peroxide, reacting at 70 deg.C for 2 hr, recovering to room temperature, precipitating with ethanol, filtering, washing the obtained solid with water to neutrality, and drying.
The method for modifying the carbon fiber by the coupling agent KH-560 comprises the following steps:
mixing KH-560 with water, performing ultrasonic treatment for 0.5h, adding methanol, performing ultrasonic treatment for 0.5h to obtain hydrolyzed KH-560, and adding carbon fiber into ethanol/water at a mass ratio of 1: 1, uniformly mixing the components in a mixed solvent consisting of 1, heating to 65 ℃, adding hydrolyzed KH-560, reacting for 30min under heat preservation, filtering, and drying the obtained solid.
The preparation method of the marine high-strength tear-resistant rubber material comprises the following steps:
mixing and plasticating natural rubber, epoxidized natural rubber, aminated solution-polymerized styrene-butadiene rubber and epoxidized butadiene rubber, mixing and banburying the mixture with liquid polyisoprene rubber, white carbon black and carbon black for 90s, adding a coupling agent KH-560 modified carbon fiber, zinc oxide, sulfur, a vulcanizing agent DCP, an accelerator NS, an accelerator DM, an antioxidant KY-616 and an antioxidant 802, continuously banburying for 240s, thinly passing and triangularly wrapping a lower sheet, standing for 24h, and vulcanizing at 140 ℃ and 15MPa for 10 min.
Comparative example 1:
essentially the same as in example 1, except that epoxidized natural rubber was not added.
Comparative example 2:
substantially the same as in example 1 except that the prepared aminated solution-polymerized styrene-butadiene rubber was replaced with a solution-polymerized styrene-butadiene rubber.
Comparative example 3:
substantially the same as in example 1 except that butadiene rubber was used in place of the epoxidized butadiene rubber prepared.
Comparative example 4:
substantially the same as in example 1 except that carbon nanotubes were used instead of the prepared coupling agent KH-550 modified carbon nanotubes.
And (3) performance testing:
the rubber materials prepared according to the formulations and methods of examples 1 to 5 and comparative examples 1 to 4 of the present invention were used as samples for performance tests.
Tensile strength and elongation at break: the test was performed according to GB/T528-.
Wear resistance: the test was carried out according to GB/T1689-1998.
Tear strength: the test was performed according to GB/T529-2008.
The test results are shown in table 1 below:
table 1:
salt spray corrosion resistance: the test is carried out according to GB/T35858-2018, the experimental temperature is 35 ℃, the salt spray solution is a sodium chloride solution with the concentration of 5%, and the test sample is parked for 7d in the salt spray.
The test results are shown in table 2 below:
wherein "+" represents increase and "-" represents decrease;
table 2:
as can be seen from the above table 1, the rubber material prepared by the invention has good mechanical properties, and the addition of the epoxidized natural rubber, the aminated solution-polymerized styrene-butadiene rubber, the liquid polyisoprene rubber, the epoxidized butadiene rubber and the coupling agent modified one-dimensional carbon nanomaterial has a positive effect on improving the mechanical properties of the rubber material;
as can be seen from the above table 2, the rubber material prepared by the invention has good salt spray corrosion resistance, and the comparison shows that the addition of the epoxidized natural rubber, the aminated solution-polymerized styrene-butadiene rubber, the liquid polyisoprene rubber, the epoxidized butadiene rubber and the coupling agent modified one-dimensional carbon nanomaterial plays a positive role in improving the salt spray corrosion resistance of the rubber material, particularly the addition of the aminated solution-polymerized styrene-butadiene rubber and the epoxidized butadiene rubber, the amino group can be grafted with the epoxy group in a covalent form to improve the crosslinking density of the rubber material, and the addition of the coupling agent modified one-dimensional carbon nanomaterial can play a role in toughening and reinforcing, and the modification of the surface has better compatibility with the rubber matrix, so that the gaps generated by agglomeration are reduced, and the function of improving the salt spray corrosion resistance is achieved.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. The high-strength tear-resistant rubber material for the ship is characterized by comprising the following components in parts by weight:
40-60 parts of natural rubber, 5-10 parts of epoxidized natural rubber, 20-30 parts of aminated solution-polymerized styrene-butadiene rubber, 20-30 parts of liquid polyisoprene rubber, 10-15 parts of epoxidized butadiene rubber, 15-20 parts of coupling agent modified one-dimensional carbon nano material, 5-8 parts of white carbon black, 5-8 parts of carbon black, 5-10 parts of zinc oxide and 0.1-1 part of auxiliary agent;
the preparation method of the aminated solution polymerized styrene-butadiene rubber comprises the following steps:
under the protection of inert gas, uniformly mixing butadiene, styrene, an amination reagent and cyclohexane, diluting butyl lithium with tetrahydrofuran, adding the diluted butyl lithium, controlling the reaction temperature to be 45-50 ℃, reacting for 8-12h, performing wet devolatilization, and drying;
the amination reagent is 4-aminostyrene, 4-dimethylaminostyrene or 1, 1-bis (4-dimethylaminophenyl) ethylene.
2. The marine high strength tear resistant rubber material of claim 1, wherein the mass ratio of butyl lithium to tetrahydrofuran is 1: 60-80.
3. The marine high strength, tear resistant rubber material of claim 1 wherein the epoxidized butadiene rubber is prepared by the following process:
adding butadiene rubber into cyclohexane, adding formic acid and polyethylene glycol, stirring, adding hydrogen peroxide, reacting at 70-75 deg.C for 1.5-2h, recovering to room temperature, precipitating with ethanol, filtering, washing the obtained solid with water to neutrality, and drying.
4. The marine high-strength tear-resistant rubber material according to claim 1, wherein the coupling agent-modified one-dimensional carbon nanomaterial is a coupling agent-modified carbon nanotube or a coupling agent-modified carbon nanofiber.
5. The marine high strength tear resistant rubber material of claim 4, wherein the coupling agent is a coupling agent KH-550, KH-560, or KH-570;
the method for modifying the one-dimensional carbon nano material by the coupling agent comprises the following steps:
adding the one-dimensional carbon nano material into an ethanol/water mixed solvent, uniformly mixing, heating to 60-65 ℃, adding the hydrolyzed coupling agent, reacting for 20-40min under the condition of heat preservation, filtering, and drying the obtained solid.
6. The marine high strength tear resistant rubber material of claim 1 wherein the auxiliary agent comprises sulfur, vulcanizing agent DCP, accelerator NS, accelerator DM, antioxidant KY-616 and antioxidant 802.
7. A process for the preparation of a marine high strength tear resistant rubber material according to any one of claims 1 to 6,
mixing and plasticating natural rubber, epoxidized natural rubber, aminated solution-polymerized styrene-butadiene rubber and epoxidized butadiene rubber, mixing and banburying the mixture with liquid polyisoprene rubber, white carbon black and carbon black for 30-90s, adding a coupling agent modified one-dimensional carbon nano material, zinc oxide and an auxiliary agent, continuously banburying for 180-240s, thinly passing and wrapping a piece by a triangular bag, standing for 12-24h, and vulcanizing at 140-150 ℃ and 10-15MPa for 10-20 min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10256790A1 (en) * | 2002-12-05 | 2004-06-17 | Degussa Ag | Continuous process for the production of rubber granules containing fillers |
| JP2009102507A (en) * | 2007-10-23 | 2009-05-14 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread |
| CN104271359A (en) * | 2012-03-02 | 2015-01-07 | 卡博特公司 | Elastomeric composites containing modified fillers and functionalized elastomers |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10256790A1 (en) * | 2002-12-05 | 2004-06-17 | Degussa Ag | Continuous process for the production of rubber granules containing fillers |
| JP2009102507A (en) * | 2007-10-23 | 2009-05-14 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread |
| CN104271359A (en) * | 2012-03-02 | 2015-01-07 | 卡博特公司 | Elastomeric composites containing modified fillers and functionalized elastomers |
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